Pe wax dispersions in the coating of plastics

ABSTRACT

An aqueous paint formulation composed of an aqueous basecoat and an aqueous dispersion of an at least partially neutralized ethylene copolymer wax which is selected from ethylene copolymer waxes comprising as comonomers in copolymerized form:
         (A) 12% to 40% of an ethylenically unsaturated carboxylic acid of the formula I,       

     
       
         
         
             
             
         
       
         
         
           
             
               
                 where 
                 R 1  and R 2  are hydrogen and/or C 1 -C 10 alkyl; 
               
             
             (B) 60% to 88% of ethylene; 
             (C) 0% to 10% of a further comonomer; or 
             (A′) 5% to 50% of a comonomer of the formula II 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             
               
                 where 
                 R 1  and R 2  are hydrogen and/or C 1 -C 10 alkyl, 
                 R 3  is hydrogen, C 1 -C 10 alkyl and/or C 3 -C 12 cycloalkyl, where two radicals R 3  may be joined to form a ring, 
                 X is oxygen, sulfur and/or N—R 4 , 
                 R 4  is C 1 -C 10 alkyl or hydrogen, and 
                 A 1  is a divalent group; 
               
             
             (B′) 50% to 95% by weight of ethylene, and 
             (C′) zero to 20% by weight of a further comonomer;
           where the ethylene copolymer waxes (A)(B)(C) and (A′)(B′)(C′) have a molecular weight 10 000 to 100 000 and 5000 to 40 000 g/mol, respectively;   and the use thereof for coating plastics.

The invention relates to an aqueous paint formulation comprising atleast one aqueous basecoat and at least one aqueous dispersion of atleast one specific ethylene copolymer wax, and to the use thereof forcoating plastics.

Plastics moldings are used in numerous areas, such as in automobiles, inthe household, etc. The painting of plastics moldings often isdifficult, since typical coating materials adhere poorly to plasticsmaterials. In particular, the painting of nonpolar plastics materialssuch as polypropylene (PP) and thermoplastic olefins (TPO) presentsdifficulties. Consequently, a primer layer comprising anadhesion-promoter system is often applied to the cleaned plasticssurface, and this boosts the adhesion between the surface and abasecoat. The formulation used for the primer coat frequently comprisesorganic solvents and chlorinated polyolefins (CPO). Over the primercoat, the basecoat and, where used, a clearcoat are then applied. InEurope, both basecoat and clearcoat are primarily water-based.

U.S. Pat. No. 3,637,428 describes substrates based on copolymers ofethylene and a polar comonomer, which are coated with a basecoatformulation comprising the film-forming resin, a vinyl acetate polymeras adhesion promoter, and an organic solvent. Disadvantages are the useof an organic solvent and the fact that the coating is suitable only forvery specific substrates.

U.S. Pat. No. 5,585,192 describes a water-based formulation forpromoting adhesion, comprising a maleinized polyolefin and a polyolefinwax. As a primer coat, the formulation boosts the adhesion betweenpolymer substrates of PP, TPO, and PE, and a basecoat.

For enhancing the adhesion of paints to PP and TPO surfaces, the companyEastman markets the product Advantis® 510W (®=registered trademark),which is an aqueous dispersion of a halogen-free polyolefin adhesionpromoter. Advantis® 510W can be mixed directly with aqueous paintformulations based on acrylic or on polyurethane, and applied as amixture to a plastics substrate.

US-A-20030018139 discloses solventborne and aqueous primer formulationscomprising a carboxylated polyolefin which is modified withpolyfunctional alcohols. The polyolefin is preferably apropylene-ethylene copolymer grafted with carboxyl-containing monomers,preferably maleic anhydride, and modified fully or partly by reactionwith a polyfunctional alcohol. Aqueous emulsions are obtained byneutralizing some of the carboxyl groups with an amine or an inorganicbase. The aforementioned reaction products are used as primers, andimprove the adhesion of paints to plastics substrates such as TPO. Alsodescribed are mixtures of the basecoat with the alcohol-modified,carboxylated polyolefin, which can be applied in this form to asubstrate.

On grounds of costs, attempts are increasingly being made to do withoutthe primer coat, while nevertheless ensuring satisfactory adhesion of awaterborne basecoat to a plastics surface.

It is an object of the invention, therefore, to provide improvedplastics coatings which meet the aforementioned requirements.

It has now been found that aqueous basecoat formulations whichadditionally comprise aqueous dispersions based on specific polyethylenecopolymer waxes are distinguished by particularly effective promotion ofadhesion in the context of the coating of plastics.

The invention accordingly provides an aqueous paint formulation composedof at least one aqueous basecoat and at least one aqueous dispersion ofat least one at least partially neutralized ethylene copolymer wax whichis selected from ethylene copolymer waxes comprising as comonomers incopolymerized form:

-   (A) 12% to 40%, preferably 20% to 35%, by weight of at least one    ethylenically unsaturated carboxylic acid of the general formula I,

-   -   where    -   R¹ and R² are selected independently of one another from        hydrogen and unbranched and branched C₁-C₁₀alkyl;

-   (B) 60% to 88%, preferably 80% to 65%, by weight of ethylene;

-   (C) 0% to 10%, preferably 0% to 5%, by weight of at least one    further comonomer; or

-   (A′) 5% to 50%, preferably 20% to 40%, by weight of at least one    comonomer of the general formula II

-   -   where    -   R¹ and R² are selected independently of one another from        hydrogen and unbranched and branched C₁-C₁₀alkyl,    -   R³ is selected independently at each occurrence from hydrogen,        unbranched and branched C₁-C₁₀alkyl, and C₃-C₁₂cycloalkyl, where        two radicals R³ may be joined to one another to form a 3- to        10-membered ring,    -   X is selected from oxygen, sulfur, and N—R⁴,    -   R⁴ is selected from unbranched and branched C₁-C₁₀alkyl and        hydrogen, and    -   A¹ is a divalent group selected from C₁-C₁₀alkylene,        C₄-C₁₀cycloalkylene, and phenylene;

-   (B′) 50% to 95% by weight of ethylene, preferably 60% to 80% by    weight, and

-   (C′) zero to 20% by weight, preferably zero to 10% by weight, of at    least one further comonomer;    where the ethylene copolymer wax comprising the comonomers (A), (B),    and optionally (C) has a molecular weight M_(w) of 10 000 to 150 000    g/mol, and the ethylene copolymer wax comprising the comonomers    (A′), (B′), and optionally (C′) has a molecular weight M_(w) of 5000    to 40 000 g/mol.

Comonomers (A), (B), and (C), and (A′), (B′), and (C′), that arecomprised in copolymerized form are those fractions of comonomer whichare incorporated molecularly into the ethylene copolymer waxes used inaccordance with the invention, and add up to 100% by weight.

The fraction of the aqueous ethylene copolymer wax dispersion in thepaint formulation of the invention is generally 0.1% to 10%, preferably0.5% to 5%, more preferably 1% to 3%, by weight, based on the aqueousbasecoat.

An ethylene copolymer used in accordance with the invention andcomprising comonomer (A′) in copolymerized form may be present withpartial protonation or as the free amine.

In the formulae I and II the variables are defined as follows:

R¹ and R² are the same or different;R¹ is selected from hydrogen andunbranched and branched C₁-C₁₀alkyl, such as, for example, methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl,n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl,n-decyl; more preferably C₁-C₄alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, moreparticularly methyl;R² is selected from unbranched and branched C₁-C₁₀alkyl such as, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl,n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably C₁-C₄alkyl suchas methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, andtert-butyl, particularly methyl,and very preferably hydrogen;the radicals R³ are different or preferably the same and are selectedfrom hydrogen and branched and preferably unbranched C₁-C₁₀alkyl suchas, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl,n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; preferably methyl, ethyl,n-propyl, n-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl; more preferably C₁-C₄alkyl such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, verypreferably methyl;C₃-C₁₂cycloalkyl such as, for example, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, and cyclododecyl; preferably cyclopentyl,cyclohexyl, and cycloheptylwhere two radicals R³ may be joined to one another to form a 3- to10-membered, preferably 5- to 7-membered, ring which is optionallysubstituted by C₁-C₄alkyl radicals, with particular preference a groupN(R³)₂ may be selected from

If the radicals R³ are different, then one of the radicals R³ may behydrogen.

X is selected from sulfur, N—R⁴, and, in particular, oxygen.

R⁴ is selected from hydrogen and unbranched and branched C₁-C₁₀alkylsuch as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, preferably hydrogenand C₁-C₄alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, and tert-butyl, more preferably methyl, andhydrogen;A′ is selected from divalent groups such asC₁-C₁₀alkylene, such as, for example, —CH₂—, —CH(CH₃)—, —(CH₂)₂—,—CH₂—CH(CH₃)—, cis- and trans-CH(CH₃)—CH(CH₃)—, —(CH₂)₃—,—CH₂—CH(C₂H₅)—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, —(CH₂)₇—, —(CH₂)₈—,—(CH₂)₉—, —(CH₂)₁₀—; preferably C₂-C₄alkylene, such as —(CH₂)₂—,—CH₂—CH(CH₃)—, —(CH₂)₃—, —(CH₂)₄—, and —CH₂—CH(C₂H₅)—, more preferably—(CH₂)₂—, —(CH₂)₃—, and —(CH₂)₄—, very preferably —(CH₂)₂—;C₄-C₁₀cycloalkylene such as, for example,

preferably

in isomerically pure form or as an isomer mixture,andphenylene, as for example ortho-phenylene, meta-phenylene, and, withparticular preference, para-phenylene.

In one embodiment of the present invention R¹ is hydrogen or methyl.Very preferably R¹ is methyl.

In one embodiment of the present invention R¹ is hydrogen or methyl andR² is hydrogen. Comonomer (A) very preferably is methacrylic acid.

In one embodiment of the present invention R¹ is hydrogen or methyl andR² is hydrogen, both groups R³ are the same and are in each case methylor ethyl.

In one embodiment of the present invention X-A¹-N(R³)₂ isO—CH₂—CH₂—N(CH₃)₂. Comonomer (A′) very preferably is dimethylaminoethylmethacrylate.

In one embodiment of the present invention X-A¹-N(R³)₂ isO—CH₂—CH₂—CH₂—N(CH₃)₂.

In one embodiment of the present invention comonomer (A′) is inprotonated form.

In one embodiment of the present invention the ethylene copolymercomprises no further comonomers (C) or (C′) in copolymerized form.

In another embodiment of the present invention the ethylene copolymercomprises, in addition to the comonomers (A) and (B), at least onefurther comonomer (C) as well in copolymerized form, selected from: (c1)ethylenically unsaturated C₃-C₁₀ carboxylic esters, (c2) ethylenicallyunsaturated C₄-C₁₀ dicarboxylic acids or their anhydrides, and (c3)epoxide esters of ethylenically unsaturated C₃-C₁₀ monocarboxylic acids.

Ethylenically unsaturated C₃-C₁₀ carboxylic esters (c1) are, forexample, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl(meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,n-octyl (meth)acrylate, n-decyl (meth)acrylate, and/or 2-propylheptyl(meth)acrylate.

Used very preferably as ethylenically unsaturated carboxylic esters (c1)are methyl acrylate and/or methyl methacrylate.

Ethylenically unsaturated C₄-C₁₀ dicarboxylic acids (c2) include, forexample, itaconic acid, mesaconic acid, citraconic acid, fumaric acid,and, in particular, maleic acid. Examples of their anhydrides includeitaconic anhydride and, in particular, maleic anhydride.

Examples of epoxide esters of ethylenically unsaturated C₃-C₁₀monocarboxylic acids (c3) include, in particular, esters of crotonicacid and/or (meth)acrylic acid with glycidol, preferably glycidylacrylate and especially glycidyl methacrylate.

Used very preferably as ethylenically unsaturated carboxylic esters (c1)are methyl acrylate and/or methyl methacrylate.

In another embodiment of the present invention the ethylene copolymercomprises, in addition to the comonomers (A′) and (B′), at least onefurther comonomer (C′) as well in copolymerized form, selected from:

(c′1) C₁-C₂₀alkyl esters of ethylenically unsaturated C₃-C₁₀monocarboxylic acids, also called, for short, ethylenically unsaturatedC₃-C₂₀ carboxylic esters, examples being methyl (meth)acrylate, ethyl(meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate,2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl(meth)acrylate, 2-propylheptyl (meth)acrylate;(c′2) mono- and di-C₁-C₁₀alkyl esters of ethylenically unsaturatedC₄-C₁₀ dicarboxylic acids, examples being monomethyl and dimethylmaleate, monoethyl and diethyl maleate, monomethyl and dimethylfumarate, monoethyl and diethyl fumarate, monomethyl and dimethylitaconate, mono-n-butyl and di-n-butyl maleate, and mono-2-ethylhexyland di-2-ethylhexyl maleate;(c′3) vinyl esters or allyl esters of C₁-C₁₀ carboxylic acids,preferably vinyl esters or allyl esters of acetic acid or propionicacid, more preferably vinyl propionate and vinyl acetate, and verypreferably vinyl acetate;(c′4) epoxide esters of ethylenically unsaturated C₃-C₁₀ monocarboxylicacids, more particularly esters of crotonic acid and/or (meth)acrylicacid with glycidol, preferably glycidyl acrylate and especially glycidylmethacrylate; and(c′5) anhydrides of ethylenically unsaturated dicarboxylic acids such asitaconic anhydride and especially maleic anhydride.

The ethylene copolymer formed from the comonomers (A) and (B) or (A′)and (B′) preferably comprises, as comonomer (C) or (C′), maleicanhydride and/or glycidyl methacrylate.

In one embodiment of the present invention comonomer (A) is inneutralized form.

The ethylene copolymer waxes employed in the dispersions used inaccordance with the invention, and comprising the comonomers (A), (B),and, optionally, (C), have in general a melt flow rate (MFR) in therange from 1 to 50 g/10 min, preferably 5 to 20 g/10 min, morepreferably 7 to 15 g/10 min, measured at 160° C. under a load of 325 gin accordance with EN ISO 1133. Their acid number is typically 50 to 200mg KOH/g copolymer, preferably 100 to 200 mg KOH/g copolymer, determinedin accordance with DIN 53402.

The molecular weight M_(w) of the ethylene copolymer waxes employed inthe dispersions used in accordance with the invention, and comprisingthe comonomers (A), (B), and, optionally, (C), is in general from 10 000to 150 000 g/mol, preferably from 20 000 to 120 000 g/mol, morepreferably from 50 000 to 100 000 g/mol.

The melting ranges of the ethylene copolymer waxes employed in thedispersions used in accordance with the invention, and comprising thecomonomers (A), (B), and, optionally, (C), are situated in general inthe range from 60 to 110° C., preferably in the range from 70 to 90° C.,as determined by DSC in accordance with DIN 51007.

The ethylene copolymer waxes employed in the dispersions used inaccordance with the invention, and comprising the comonomers (A), (B),and, optionally, (C), may be alternating copolymers or block copolymersor, preferably, gradient or random copolymers.

The molecular weight M_(w) of the ethylene copolymer waxes employed inthe dispersions used in accordance with the invention, and comprisingthe comonomers (A′), (B′), and, optionally, (C′), is from 5000 to 40 000g/mol, preferably from 10 000 to 30 000 g/mol, more preferably from 15000 to 25 000 g/mol.

The melting point of the ethylene copolymer waxes employed in thedispersions used in accordance with the invention, and comprising thecomonomers (A′), (B′), and, optionally, (C′), is situated in general inthe range from 40 to 100° C., preferably in the range from 40 to 80° C.,as determined by DSC in accordance with DIN 51007.

The ethylene copolymer waxes used can be prepared by conventionalprocesses for copolymerizing ethylene (B) or (B′), comonomer (A) or(A′), and, optionally, further comonomers (C) or (C′), in stirredhigh-pressure autoclaves or in high-pressure tube reactors. Preparationin stirred high-pressure autoclaves is preferred. Stirred high-pressureautoclaves are known: a description is found in, for example, Ullmann'sEncyclopedia of Industrial Chemistry, 5th edition, entry heading: Waxes,volume A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, NewYork, Tokyo, 1996. The length/diameter ratio of such autoclaves ispredominantly in ranges from 5:1 to 30:1, preferably 10:1 to 20:1. Thehigh-pressure tube reactors which may likewise be employed are foundlikewise in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition,entry heading: Waxes, volume A 28, p. 146 ff., Verlag Chemie Weinheim,Basel, Cambridge, New York, Tokyo, 1996. Details on the preparation ofethylene copolymer are also given in WO 2008/101937.

The preparation of aqueous dispersions of ethylene copolymer waxes isknown per se. A preferred procedure is to place one or more ethylenecopolymers in a vessel together with further substances, the vesselbeing, for example, a flask, an autoclave or a tank, and to heat thecontents.

In the case of ethylene copolymer waxes comprising the comonomers (A′),(B′), and, optionally, (C′), one or more Brønsted acids such as, forexample, organic acids like glacial acetic acid, formic acid, lacticacid, butyric acid, benzoic acid, methanesulfonic acid, andpara-toluenesulfonic acid, or inorganic acids like nitric acid,hydrochloric acid, phosphoric acid, and sulfuric acid, and water, andoptionally further substances, examples being emulsifiers, are added,the sequence of addition of Brønsted acid or Brønsted acids and also,where used, further substances being arbitrary.

The amount of Brønsted acid added is such that the ethylene copolymer isin partially or, preferably, fully neutralized form. In one embodimentof the present invention an excess of Brønsted acid is used.

If comonomer (A′) in the ethylene copolymer wax comprising thecomonomers (A′), (B′), and, optionally, (C′) is already in at leastpartly protonated form, it may not be necessary to add Brønsted acid.

In the case of ethylene copolymer waxes synthesized from the comonomers(A), (B), and, optionally, (C), it is usual to add one or more basicsubstances, with which the ethylene copolymer waxes are at least partlyneutralized, examples being hydroxides and/or carbonates and/or hydrogencarbonates of alkali metals, or preferably amines such as, for example,ammonia and organic amines such as, for example, alkylamines,N-alkylethanolamines, alkanolamines and polyamines. Examples ofalkylamines include the following: triethylamine, diethylamine,ethylamine, trimethylamine, dimethylamine, methylamine. Preferred aminesare monoalkanolamines, N,N-dialkylalkanolamines, N-alkylalkanolamines,dialkanolamines, N-alkyldialkanolamines, and trialkanolamines having ineach case 2 to 18 C atoms in the hydroxyalkyl radical and optionally ineach case 1 to 6 C atoms in the alkyl radical, preferably 2 to 6 C atomsin the alkanol radical, and optionally 1 or 2 C atoms in the alkylradical. Especially preferred are ethanolamine, diethanolamine,triethanolamine, methyldiethanolamine, n-butyldiethanolamine,N,N-dimethylethanolamine, and 2-amino-2-methylpropan-1-ol. Especiallypreferred are ammonia and N,N-dimethylethanolamine. Examples ofpolyamines include the following: ethylenediamine,tetramethylethylenediamine (TMEDA), diethylenetriamine, andtriethylenetetramine.

In one embodiment of the present invention dispersions of ethylenecopolymer waxes used in accordance with the invention and synthesizedfrom the comonomers (A), (B), and, optionally, (C) comprise an amount ofbasic substance or basic substances such that at least half, preferablyat least 60 mol %, of the carboxyl groups in the ethylene copolymer waxor waxes are neutralized.

In one embodiment of the present invention dispersions of ethylenecopolymer waxes used in accordance with the invention and synthesizedfrom the comonomers (A), (B), and, optionally, (C) comprise basicsubstance or basic substances, and more particularly amine, in an amountsuch that the carboxyl groups of the ethylene copolymer wax or waxes areneutralized quantitatively.

In one embodiment of the present invention dispersions of ethylenecopolymer waxes used in accordance with the invention and synthesizedfrom the comonomers (A), (B), and, optionally, (C) may comprise morebasic substance or basic substances, more particularly amine, than is orare necessary for complete neutralization of the ethylene copolymer waxor waxes—for example, an excess of up to 100 mol %, preferably up to 50mol %.

If it is desired to prepare the dispersion in question at a temperatureabove 100° C., it is advantageous to operate under increased pressureand to select the vessel accordingly. The dispersion formed ishomogenized, by mechanical or pneumatic stirring or by shaking, forexample. It is advantageously heated to a temperature above the meltingpoint of the ethylene copolymer wax. Heating takes place advantageouslyto a temperature which is at least 10° C., more advantageous to atemperature which is at least 30° C., above the melting point of theethylene copolymer wax.

The aqueous dispersions used in accordance with the invention have asolids content in the range from 5% to 40%, preferably 10% to 30%, byweight. The water used for the dispersions is preferably deionized,i.e., purified by distillation or by means of an ion exchanger.

The pH of the aqueous dispersions comprising ethylene copolymer waxessynthesized from comonomers (A), (B), and, optionally, (C) is generally7 to 14, preferably 8 to 10.

The pH of the aqueous dispersions comprising ethylene copolymer waxessynthesized from comonomers (A′), (B′), and, optionally, (C′) isgenerally 1 to 7, preferably 3 to 6.

The aforementioned aqueous ethylene copolymer wax dispersions are usedin accordance with the invention, with typical waterborne basecoatmaterials, to prepare the aqueous modified paint formulations of theinvention. For this purpose, the aforementioned aqueous ethylenecopolymer wax dispersions are admixed directly to commercial aqueouspaint formulations (i.e., basecoat) based, for example, on polyurethane,polyester, alkyd, melamine and/or polyacrylate resins.

Further provided by the invention is the use of the aqueous modifiedpaint formulations of the invention for coating plastics. The plasticsmay be moldings from many different sectors. Examples from theautomobile sector include, for example, bumpers, tank covers, etc.Examples from the household sector are small appliances, packaging,toys, etc. Examples of plastics materials used for this purpose includepolyurethanes, polyamides, polycarbonates, polyesters, and, inparticular, nonpolar plastics materials. Examples of the latter arepolyolefins such as polyethylene, ethylene copolymers, polypropylene,propylene copolymers, polyolefin mixtures with other polymers, such asPP/EPDM blends, for example, and PVC.

For coating, the cleaned and dried plastics surfaces are provided withthe modified basecoat formulation. The substrate may be coated in avariety of ways, for example by dipping, spraying or application of themodified basecoat formulation. Over this basecoat formulation it is thenpossible to apply a topcoat, generally a clearcoat. The film thicknessof the basecoat and of the clearcoat is dependent on the particularapplication and may vary considerably.

The plastics surfaces provided with the modified basecoat formulationare notable for particularly good adhesion of the paint.

EXAMPLES Preparation of the Ethylene Copolymers

In a high-pressure autoclave of the type described in the literature (M.Buback et al., Chem. 1 ng. Tech. 1994, 66, 510), ethylene and eitherN,N-dimethylaminoethyl methacrylate (DMAEMA) or methacrylic acid (MAA)were copolymerized continuously at temperatures of 200 to 250° C.Ethylene was fed continuously into the high-pressure autoclave under thereaction pressure. Separately from this, the copolymer, optionallydiluted with isododecane, was fed continuously into the high-pressureautoclave. Separately from this, the initiator solution, consisting oftert-amyl peroxypivalate dissolved in isododecane, is fed continuouslyinto the high-pressure autoclave. Separately from this, where used,propionaldehyde is fed continuously into the high-pressure autoclave.The pressure during polymerization was 1500 to 2500 bar. This gaveethylene copolymers having the analytical data evident from table 1.

TABLE 1 Analytical data of ethylene copolymers used Amount Amount ofAmount of of Amount Melting ethylene DMAEMA ethylene of MAA point η Ex.No. [% by wt.] [% by wt.] [% by wt.] [% by wt.] [° C.] Mw [g/mol] [mPa ·s] 1 63 37 — — 49 17 000   2600 2 69 31 — — 41 21 700   7100 3 — — 73 2780 90 000 >50 000

By “amount” is meant the fraction of copolymerized MAA or DMAEMA,respectively, in the particular ethylene copolymer. The amount of MAAand of N,N-dimethylaminoethyl methacrylate in the ethylene copolymerswas determined by ¹H NMR spectroscopy.

η: Dynamic melt viscosity, measured at 120° C. in a plate/coneviscometer (PP 35 Ti) with a 1.0 mm gap, and D=10 [1/s] in accordancewith DIN 53018-1

Preparation of Aqueous Dispersions of the Ethylene Copolymers

A 2-liter autoclave with anchor stirrer was charged in each case withthe amount of ethylene copolymer from examples 1 to 3 which is indicatedin table 2. This initial charge was heated to 130° C. with stirring andsubsequently the amount of acid or amine (feed 1) indicated in table 2was added dropwise over the course of 15 minutes. Thereafter, over thecourse of 30 minutes, the remaining amount of water (feed 2) was added,and stirring was continued at 130° C. (external temperature) for 15minutes. After that the external temperature was lowered to 100° C., themixture was stirred at 100° C. for an hour, and was then cooled to roomtemperature over the course of 15 minutes. Filtration through a Perlonfilter (100 μm) gave the corresponding aqueous dispersions.

TABLE 2 Ethylene copolymer dispersions Amount Copoly- Glacial acetic ofH₂O Solids mer Amount acid DMEA [g], pH of content No. ex. of (B) [g]Feed 1 Feed 1 Feed 2 emulsion [% by wt.] D.1 1 225 32 g — 800 4.9 20 in69 ml H₂O D.2 2 225 28 g — 800 4.6 20 in 72 ml H₂O D.3 3 225 — 38 g 6489.0 21 in 114 ml H₂OCoating of Plastics Surfaces with Modified Basecoat Formulation

Plastics plaques measuring 15×20 cm made from PP/EPDM were cleaned withisopropanol and then dried. Each commercial basecoat formulationcomprising PU, melamine, and polyacrylate resins was admixed with theabove-described ethylene copolymer dispersions D.1 to D.3 inconcentrations of 0.5%/1.0%/5.0% by weight. The cleaned plasticssurfaces were coated with each modified basecoat formulation. Thesurfaces were flamed and coated with a clearcoat. The completed coatedplastics, plaques were flamed again. For application of the basecoatformulation, a 90 μm box coater and, for the clearcoat, a 100 μm rodcoater were used. This gave an overall dry film thickness of 70 μm. As acontrol, a plastics plaque was coated only with the basecoat formulationwithout addition of the above-described ethylene copolymer dispersionsand clearcoat.

The plaques were scored with a knife in two parallel lines bothhorizontally and vertically. The quality of the adhesion was tested inaccordance with DIN 55662 in a steam jet test. The results of the steamjet test have been summarized in FIG. 1. FIG. 1 shows, in table form,images of the plastics plaques thus treated. For purposes of comparison,the aforementioned control (1) is shown above the table. In the columnsof the table, the respective concentration (conc.) of the ethylenecopolymer dispersions in the basecoat formulation is indicated in % byweight. In the rows of the table (K.1 to K.3), the ethylene copolymerdispersion used in each case (D.1 to D.3) is indicated.

FIG. 1 shows that the modified basecoat formulations used in accordancewith the invention significantly increase the adhesion to the plasticsplaque. Particularly good adhesion was obtained with basecoatformulations comprising D.1.

1. An aqueous paint formulation composed of at least one aqueousbasecoat and at least one aqueous dispersion of at least one at leastpartially neutralized ethylene copolymer wax which is selected fromethylene copolymer waxes comprising as comonomers in copolymerized form:(A) 12% to 40%, preferably 20% to 35%, by weight of at least oneethylenically unsaturated carboxylic acid of the general formula I,

where R¹ and R² are selected independently of one another from hydrogenand unbranched and branched C₁-C₁₀alkyl; (B) 60% to 88%, preferably 80%to 65%, by weight of ethylene; (C) 0% to 10%, preferably 0% to 5%, byweight of at least one further comonomer; or (A′) 5% to 50%, preferably20% to 40%, by weight of at least one comonomer of the general formulaII

where R¹ and R² are selected independently of one another from hydrogenand unbranched and branched C₁-C₁₀alkyl, R³ is selected independently ateach occurrence from hydrogen, unbranched and branched C₁-C₁₀alkyl, andC₃-C₁₂cycloalkyl, where two radicals R³ may be joined to one another toform a 3- to 10-membered ring, X is selected from oxygen, sulfur, andN—R⁴, R⁴ is selected from hydrogen and unbranched and branchedC₁-C₁₀alkyl, and A¹ is a divalent group selected from C₁-C₁₀alkylene,C₄₋₁₀cycloalkylene, and phenylene; (B′) 50% to 95% by weight ofethylene, preferably 60% to 80% by weight, and (C′) zero to 20% byweight, preferably zero to 10% by weight, of at least one furthercomonomer; where the ethylene copolymer wax comprising the comonomers(A), (B), and optionally (C) has a molecular weight M_(w) of 10 000 to150 000 g/mol, and the ethylene copolymer wax comprising the comonomers(A′), (B′), and optionally (C′) has a molecular weight M_(w) of 5000 to40 000 g/mol.
 2. The paint formulation according to claim 1, wherein thefraction of the aqueous dispersion of the ethylene copolymer wax is 0.1%to 10% by weight, based on the aqueous basecoat.
 3. The paintformulation according to claim 1, wherein the ethylene copolymercomprises no further comonomers (C) or (C′).
 4. The paint formulationaccording to claim 1, wherein the ethylene copolymer comprises, ascomonomer (C) or (C′), maleic anhydride and/or glycidyl methacrylate. 5.The paint formulation according to claim 1, wherein the radicals in theformulae I and II have the following definitions: R¹ is hydrogen ormethyl, both groups R³ are the same and are each methyl or ethyl, and Xis oxygen.
 6. The paint formulation according to claim 1, wherein R² ishydrogen.
 7. The use of a paint formulation according to claim 1 forcoating plastics.
 8. The use according to claim 7, where the plasticsare plastics moldings from the automobile and/or household sectors.